Novel nickel alcoholates and alcohols thereof and a process of their production



United States Patent US. Cl. 260-3473 24 Claims ABSTRACT OF THEDISCLOSURE Process of producing nickel alcoholates by reacting 0 valentcomplexes of nickel with conjugated diolefins and carbonyl compounds.The nickel alcoholates can be hydrolyzed to their corresponding alcoholsand these alcohols can be dehydrated in part to corresponding olefins.The products of such reaction are also disclosed. The nickel alcoholateproducts are useful for manufacturing their corresponding alcohols. Thealcohols are useful as starting materials for the production ofpolyenes.

This invention relates to novel nickel alcoholates and alcohols thereofand to a process of preparing said novel nickel alcoholates andalcohols.

According to German patent 1,191,375, it is possible to preparecomplexes of transition metals by reducing compounds of transitionmetals with organo-metallic compounds of themetals of Groups I to III ofthe Periodic Table in the presence of electron donors. This processpermits also the preparation of complexes of zerovalent nickel such asall-trans-cyclododecatri-1,5,9-enenickel (0),bis(cyclooctadi-l,5-ne)-nickel (0), cyclooctatetraene-m'ckel (0),tetrakis(triphenyl-phosphine)nickel (0).

In further developing this process, it has been found that, indisplacement reactions, the ligands bonded to the central metal may bereplaced by other ligands. For example,all-trans-cyclododecatri-1,5,9-ene-nickel (0), reacts at as low as about60 C. with butadiene. Thereby, the cyclododecatriene is displaced andthere is formed a C -bis-ar-allyl system I bonded to nickel bycombination of three butadiene molecules each:

CDT =cyclododecatriene 3,544,604 Patented Dec. 1, 1970 hyde nickel (O)or bis(cinnamic aldehyde) nickel (O) is obtained frombis(cyclooctal-1,5-ene) nickel (0) and cinnamic aldehyde with thecleavage of cyclooctadi-1,5-ene. Analogous products are obtained withother carbonyl compounds.

It has now been found surprisingly that it is possible by thesimultaneous action of carbonyl compounds and 1,3-diolefins on complexesof zero-valent nickel to link every two molecules of the carbonylcompound with one molecule of a 1,3-diolefin thereby forming a nickelalcoholate of hexene-(3-diol-(1,6). For example, in a simple case, it ispossible to link benzaldehyde and butadiene to form the nickelate of1,6-diphenylhexene-(S-trans)-diol- (1,6) 11 according to the followingequation:

[CODhNi 20,11,0H0 04m C O D =cyclooctadiene II After hydrolysis of thenickelate, the diol which may be converted in known manner into1,6-diphenylhexatri- 1,3,5-ene is obtained in high yields.

The process according to the invention for the production of novelalcohols and nickel alcoholates thereof compnses (a) allowing carbonylcompounds and 1,3-diolefins to act on complexes of nickel (0) or (b)reacting vr-allyl nickel compounds with carbonyl compounds, thenhydrolyzing the resultant novel nickel alcoholates in known manner and,if desired, dehydrating the alcohols.

Nickel alcoholates produced according to this invention have the formulaaliphatic, alicyclic, saturated and unsaturated aldehydes and ketonesand saturated and unsaturated aldehydes and ketones which aresubstituted by aromatic radicals. Examples include formaldehyde,acetaldehyde, propionaldehyde, butyric aldehyde, acrolein,crotonaldehyde, hexadienal, propargyl aldehyde, benzaldehyde, cinnarnicaldehyde, phenylpentadienal, vitamin A aldehyde, anisic aldehyde,vanillin, acetone, methyl ethyl ketone, mesityl oxide, cyclopentanone,cyclohexanone, acetophenone, benzophenone, ,B-ionone. Aliphatic,alicyclic saturated and unsaturated dialdehydes and diketones andsaturated and unsaturated dialdehydes and diketones which aresubstituted by aromatic residues may also be used. Examples includeglyoxal, malonic dialdehyde, succinic dialdehyde, diacetyl, acetylacetone, acetonyl acetone, benzil, benzoyl acetone. When usingdialdehydes and diketones, longer chains having recurring monomericunits may be formed. Suitable 1,3-diolefins are butadiene or butadieneswhich are substituted by aliphatic, alicyclic or aromatic radicals suchas isoprene, 2,3-dimethyl butadiene, 2,3-diphenyl budtadiene. Both thecarbonyl compounds and the 1,3- diolefins may contain functional groupswhich, however, are groups which are not reactive or react very muchslower with the metal atoms than the carbonyl group or 1,3-diolefingrouping. Examples of such functional groups include ether, ester,acetyl, amine and nitrile groupings.

The process of the invention may be advantageously carried out byallowing the carbonyl compounds and the 1,3-diolefins to act directly onthe isolated complex compounds of nickel. Another particularlyadvantageous method of carrying out the process is to reduce nickelcompounds such as nickel acetyl acetonate by means of organometalliccompounds in the simultaneous presence of carbonyl compounds and1,3-diolefins according to the process described in German Patent1,191,375. The nickel atoms obtained during the reduction act then inthe same manner as the metal atoms combined in the isolated complexes.This embodiment just mentioned permits the use of catalytic amounts ofnickel in performing the reaction which normally proceedsstoichiometrically with respect to nickel because the nickelates beingproduced during the process of the invention may in turn be reduced. Theprocess remains a stoichiometric reaction with respect to theorganometallic component used.

In this reaction according to the invention, vr-allyl nickel alcoholatesare formed:

According to the invention, productsof this kind may be preparedadvantageously from bis-1r-allyl compounds of nickel and carbonylcompounds. In this manner, the C bis-1r-al1yl compound mentioned abovereacts with, for example, benzaldehyde to form a vr-allyl nickelalcoholate.

In an analogous manner, 1r-al1yl nickel-l-phenylbutene- (3)-olate (IV)is obtained from bis-1r-allyl nickel and benzaldehyde:

The process according to the invention may be carried out in thepresence of solvents such as aliphatic, alicyclic or aromatichydrocarbons, ethers or esters. However, the carbonyl compounds or the1,3-diolefins themselves may also serve as solvents. The reaction iscarried out at temperatures of from 0 to 200 C. and preferably at 20 toC. The nickel alcoholates may either be isolated and subsequentlysubjected to hydrolysis or directly hydrolyzed without being isolated.

The alcohols obtained by hydrolysis of the nickel alcoholates obtainableby the process according to the invention are valuable startingmaterials for further syntheses, especially for the production ofpolyenes. Thus, when starting from vitamin A aldehyde, butadiene andnickel, the process according to the invention gives a nickel alcoholatewhich, when hydrolyzed, furnishes a diol the dehydration of which leadsto a CI H polyene which is a homologue of beta carotin.

-|- C4115 [CODhNi l-NKOH):

5 EXAMPLE 1 9.3 grams=33.8 mmoles of (COD) Ni are suspended in 100 ml.of'ether and reacted at -30 C. with a solution of 5.0 g.=113 mmoles ofacetaldehyde in ether. Then 3 g.=55.5 mmoles of butadiene are introducedand the reaction is allowed to proceed at 20 C. After 24 hours, themixture is filtered. A light violet, sparingly soluble precipitate isobtained. The solution is almost colorless. Yield: 6.4 grams=31.8mmoles=94% of the theory.

Calculated for C H O Ni: 29.2% Ni; found, 30.1% Ni.

A portion of 3.6 g.=17.9 mmoles of the alcoholate are reacted with 100ml of aqueous alcohol (5% of water). After 2 4hours, the greensuspension is freed from the solvents at 10- mm. Hg. The green residueis extracted with ether, the extract is evaporated and the residuedistilled; B.P. =90-95 C/0.05 mm. Hg. Yield: 2.2 g. of a viscous oilwhich, according to analysis by gas chromatography, consists of 97% ofoctene(4)-doil-(2.7). Yield, 83% of the theory.

EXAMPLE 2 12.2 grams=44 mmoles of (COD) Ni are suspended in 14.7 g.=138mmoles of benzaldehyde and 200 ml. of ether. Immediately thereafter,about 6 g.=110 mmoles of butadiene are introduced. After 12 hours, 41mmoles=92% of the theory of the nickel alcoholate II are obtained as abrown precipitate.

Calculated for C H O Ni: 18.05% Ni; M -325.01. Found, 17.90% Ni;M=320.0.

4.2 grams=12.9 mmoles of II are dissolved in 50 ml. of benzene and addeddropwise to the deep red solution of 2 g.=26 mmoles acetyl acetone. Thereaction takes place immediately with the color turning green. 2.78grams=10.4 mmoles of 1,6-diphenyl-transhexene-(3)- dil-(1,6)=80% of thetheory are obtained. Melting point, 117118 C. after recrystallizationfrom benzene/ petroleum ether.

Calculated for 0, 11, 0 80.56% C., 7.51% H. Found, 80.21% C, 7.62% H.

grams=18.6 mmoles of diphenyl hexenediol are dehydrated with 5 ml. ofPOC1 in 30 ml. of anhydrous pyridine by the process of Greidinger andGrinsberg to give 2.6 g.=11.2 mmoles=60% of the theory of 1,6-diphenylhexatri-1,3,5-having a melting point of 200 C. afte rrecrystallwizationfrom benzene/ petroleum ether.

EXAMPLE 3 7.4 grams:27 mmoles of (COD) Ni are suspended in 100 ml. ofbenzene. To the suspension are added dropwise 7.3 g.=55 mmoles ofcinnamic aldehy while vigorously stirring. The brown precipitatedissolves completely upon introduction of 3 g.=55 mmoles of buta diene.Then 5.8 g.=58 mmoles of acetyl acetone are added and 7 g.=2l.9mmoles=81% of the theory of 1,10-diprenyl decatri-1,5,9-ene-diol-(3.8)are isolated. Melting point, 125-127 C. after recrystallization frombenzene/petroleum ether.

Calculated for C H O 82.46% C., 7.59% H. Found, 82.29% C., 7.57% H.

Melting of 3 g. of diphenyl decatrienediol together with 1 g. of freshlyannealed potassium bisulfate at 120 C. and extraction of the residuewith a boiling mixture of methanol and benzene gives 1.87 g.=6.6mm0les=70% of the theory of 1,10-diphenyl decaptaene-(1,3,5,7,9) meltingat 253 C.

EXAMPLE 4 When adding dropwise 16.5 g.=110 mmoles of phenyl pentadienalto the suspension of 14.3 g.=52 mmoles of (COD) Ni. in 100 ml. ofbenzene, a clear and deep red solution is initially formed. From thissolution, crystalline phenyl pentadienal-Ni. COD precipitates. Whenintroducing 7. g.=129 mmoles of butadiene, the precipitate dissolvesslowly with the color turning brown. After 24 hours of reaction, 11.6g.=116 mmoles of acetyl aceton are added dropwise and after further 24hours 7,7 g.: 23.5 mmoles=45% of the theory of light yellow crystalline1,14-diphenyl tetradecapentaene-(1,3,7,11,l3)-dio1- (5,10) are isolated.

Calculated for C H O 83.83% C., 7.59% H. Found, 83.39% C., 7.62% H.

1.0 gram=3 mmoles of diphenyl tetrad'ecapentaene diol are heated withfreshly annealed potassium bisulfate for 2 hours at 170 C. Thereafter,the mixture is thoroughly washed with hot water and repeatedly boiledwith benzene and chloroform. Upon cooling, 0.6 g.=2.4 mmoles=% of thetheory of 1,14-diphenyl-tetradecaheptaene-(1,3,5,7,9,11,13) precipitate.Melting point, 277 C. after recrystallization from chloroform.

EXAMPLE 5 A solution of 6.5 g.=22.8 mmoles of vitamine A aldehyde inbenzene was added dropwise to 3.1 g.=11.27 mmoles of (COD) Ni in 100 ml.of benzene. 3.4 grams: 62.8 mmoles of butadiene are introduced into thered solution. After a reaction time of 4 days, the solvents are removedat 1O mm. Hg, the brown residue suspended in 100 ml. of aqueous alcohol(5% of Water) and the Ni(OH) removed. 7.3 grams of C diol in the form ofan orange oil are obtained as residue.

A solution of 7.3 g. of C diol in 70 ml. of boiling benzene is mixedwith 250 mg. of N-bromosuccinimide. After a few seconds, the yellowsolution turns dark red. At the same time, water condenses in the refluxcondenser. After further 3 minutes at 80 C., th e mixture is cooled,diluted with 300 ml. of petroleum ether and suc cessively washed withsolutions of potassium iodide, sodium thiosulfate and sodium chloride.Drying of the solution over sodium sulfate and concentration gives 7.3g. of an oil which is dissolved in 18 ml. of benzene/ ethanol while hot.At 0 C., 1.0 gram of C hydrocarbon precipitates which is repeatedlyrecrystallized from benzene/ ethanol. Yield, 1.0 g.=1.7 mmoles of C H=15%, based on (COD) Ni charged. Melting point, 194-196 C.

EXAMPLE 6 A suspension of 11.9 g.=43.4 mmoles of (COD) Ni in 100 ml. ofacetone is prepared. Into the suspension, 6.0 g.=11 mmoles of butadieneare introduced at room temperature. Thereby, the yellow suspension turnsdark red. After stirring for two days, the color of the reaction mixtureturns green. At the same time, the contents of the flask solidify toform a gel. The volatile constituents are distilled off at 0.5 mm. Hg toleave 10.7 g. of a solid residue which is extracted in a soxhlet for 48hours with 100 ml. of ether. The residue sublimes at 10- mm. Hg and 70C. There are obtained 4.5 g.=26 mm0les=60% (based on nickel charged) of2,7-dirnethyloctene-(4) -diol- (2,7) Melting point 86 C.

Calculated for C H O 69.72%; C, 11.70%; H, M=172.20. Found: 69.72%;11.4%; H, M=172.

When carrying out the reaction at 70 C. in a bomb tube, the sameconversion is obtained in about 5 hours. The results correspond to thoseof the preceding experiments.

EXAMPLE 7 11 grams=20 mmoles of butadiene are introduced into asuspension of 19.55 g.=71 mmole of (COD) Ni and 125 ml. ofcyclohexanone. After as little as about 4 hours, the color turns green.The green gel-like reaction mixture is diluted with ml. of ether, shakenwith 50 ml. of 2NH SO and washed with NaHCO until it is free from acid.After drying over anhydrous Na SO excess butadiene and the ether aredistilled off from the colorless solution. Recrystallization of theresidue remaining after distillation from benzene/petroleum ether gives11.6 g.=46 mmoles=65% of the theory of colorless 1,4-di(cyclohexanolyl-l)butene-(2) having a melting point of 101 C.

Calcd for C H O (percent): C, 76.14; H, 11.10. Found (percent): C,76.59; H, 11.02.

EXAMPLE 8 12.0 grams=22 mmole of butadiene are introduced into asuspension of 20.4 g.=74 mmoles of (COD) Ni in 100 ml. of acetophenone.The (COD) Ni dissolves while the color turns red. After stirring forthree days at about 20 C., the gel-like reaction mixture which is nowgreen is diluted with 200 m1. of ether, washed with 50 ml. of

- 2 N H 80 neutralized with a NaHCO solution and dried over Na SO Afterseveral days, 3 grams of 1- methyl (1,3,5)-triphenyl-(2)benzoylcyclohexadiene- (2,4) precipitate from the yellow solution.Melting point, 136 C. after recrystallization from methanol.

Calcd for C H O (percent): C, 90.01; H, 6.14. Found (percent): C, 89.98;H, 6.20.

At 10- mm. Hg and about 20 C., butadiene, COD and acetophenone areremoved as far as possible from the mother liquor. There remain still39.5 grams from which a yellow liquid can be distilled 01f at 10- mm. Hgand a bath temperature of 140-150 C., this liquid consisting of 89% ofdypnone.

From the residue remaining at 150 C., 14 g.=63% of the theory of2,7-diphenyl-octene-(4)-diol-(2,7) are obtained. Melting point, 114 C.after recrystallization from benzene petroleum ether.

Calcd for C H O (percent): C, 81.04; H, 8.16. Found (percent): C, 81.22;H, 8.02.

EXAMPLE 9 6.8 grams=100 mmoles of isoprene are added dropwise at 20 C.to a suspension of 11.6 g.=42 mmoles of (COD) Ni in 52 g.=49.3 mmoles ofbenzaldehyde and 50 ml. of alcohol of water) while stirring. Thereaction begins instantaneously and the temperature rises to about 40 C.with the mixture becoming solid like a gel. There are obtained 7.5g.=26.6 mmoles=63% of the theory of1,6-diphenyl-(3)-methyl-hexene-(3)-diol-v (1,6) having a melting pointof 125126 C;

Calcd for C H O (percent): C, 80.81; H, 7.81. Found (percent): C, 81.08;H, 7.98.

EXAMPLE EXAMPLE 11 A solution of 1.1 g.==10 mmoles of benzaldehyde and1.0 g.=46 mmoles of 2,3-diphenyl butadiene in 10 ml. of benzene is addeddropwise to a suspension of 1.0 g: 36 mmoles of (COD) Ni in 30 ml. ofbenzene. After 24 hours, 1.0 g.=10 mmoles of acetyl acetone is added tothe dark red solution whereupon the color of the solution turns greenthrough brown. 0.7 gram=1.7 mmoles: 47% of the theory of1,3,4,6-tetraphenylhexene-(3)-diol- (1,6) having a melting point of134135 C. could be isolated.

Calcd for C H O (percent): C, 85.67; H, 6.71. Found (percent): C, 85.65;H, 6.88.

EXAMPLE 12 A solution of 3.3 g.=23.4 mmoles of bis(11-allyl)nickel in100 ml. of ether is reacted at 0 C. with 2.5 g.=23.5 mmoles ofbenzaldehyde. The mixture turns dark red. After 12 hours, the volatileconstituents are removed at 10- m. Hg. The residue weighting 5.1 g. isdissolved in 40 ml. of pentane and recrystallized at C. Yield: 3.5g.=l4.l mmoles of 1r-allyyl-nickel-1-phenyl-butene- (3 )-olate=60% ofthe theoretical yield.

Calculated for C H O Ni: 23.8% Ni, M=246.5. Found, 24.1% Ni, M=498.

3.5 grarns=14.l mmoles of the alcoholate are reacted with ml. of alcohol(5% of water). After 24 hours, the green suspension is freed from thesolvents at 10- mm. Hg. The green residue is extracted with ether andthe extract evaporated. There are obtained 1.8 g. of a viscous oilhaving a boiling point of 9697 C./0.5 mm. Hg and consisting of 96% of1-phenylbutene-3-ol according to analysis by gas chromatograph. Yield,82% of the theoretical.

EXAMPLE 13 A suspension of 11 g.=40 mmoles of (C0D) Ni in 100 ml. ofbenzene is prepared and reacted with 11 g.='80.8 mmoles of anisicaldehyde. Thereafter, about 6 g.= mmoles of butadiene are introduced.After 24 hours, a brow precipitate is formed and, after removal of thesolvent, reacted with 100 ml. of alcohol (5% of water). After 24 hours,the green suspension is freed from the solvents at 10- mm. Hg. Theresidue is extracted with ether and the extract evaporated to give 9.8g.=29.8 mmoles of 1,6-bis(4-methoxyphenyl)-hexene- (3)-diol-(l,6) =74%of the theory. Melting point, 140- 141 C. after recrystallization frombenzene and petroleum ether.

Calculated for C I-I O 73.14% C, 7.36% H. Found: 73.00% C, 7.20% H.

EXAMPLE 14 A solution is prepared from 49.5 mmoles of C H .Ni (I) andbutadiene in 200 ml. of ether and mixed at 20 C. with 15 g.=141 mmolesof benzaldehyde. A light brown voluminous precipitate separatesimmediately. After 12 hours, 4.8 g.=14.7 mmoles=29.6% of the theory ofthe sparingly soluble compound (III) are isolated.

Calculated for C H ONi: 17.9% Ni; found, 18.5% Ni.

A suspension of 2.5 g.=7.6 mmoles of III in 30 ml. of benzene prepared.When adding 15 m1. of glacial acetic acid, a deep red solution is formedwhich, after addition of about 0.1 g. of PtO is subjected to catalytichydrogenation at 50 atm. the product is processed after 24 hours. At 10-mm. Hg and -145 C., 1.4 g. of l-phenyltridecanol(1) distil as a viscousoil. Yield, 67% of the theoretical.

EXAMPLE 15 Preparation of 1,6-di(p-dimethylaminophenyl)-trans-3-hexene-1,6-diol 4.6 grams-=85 mmoles of butadiene are introduced into asuspension of 10 g.=36.4 mmoles of bis(cyclooctadiene) nickel and then10.8 g.=72.8 mmoles of p-dimethylaminobenzaldehyde are added. Themixture is stirred for 16 hours at 20 C. Then the precipitated nickelalcoholate is separated by filtration, washed and the diol liberatedwith the corresponding amount of acetyl acetone. Nickel acetyl acetonateis removed by filtration and the yellow ether solution decolorized withanimal charcoal to give 5.8 g. of a crystalline raw product and, afterrecrystallization from ether, g. of the compound C H N O correspondingto 39% of the bis(cyclooctadiene)nickel charged. Melting point, 120122C. (dec.). The structure is confirmed by IR and NMR spectra.

C, H analysis:

Calculated for C H N O (percent): C, 74.6; M, 8.54; N, 7.90. Found(percent): C, 75.1; H, 8.62; N, 7.85.

EXAMPLE 16 Preparation of 1,6-di(2-furyl)-trans-3-hexene-1,6-diol 4grams=74.0 mmoles of butadiene are introduced into a suspension ofg.=36.4 mmoles of bis(cyclooctadiene) nickel in 70 ml. of ether. Then 7g.=72.8 mmoles of furfural are added at a time and the mixture stirredfor 24 hours a 20 C. The nickel alcoholate is formed as a wineredprecipitate which is removed by filtration and washed with ether. Thediol is liberated with the corresponding amount of acetyl acetonewhereby nickel acetyl acetonate is obtained. Processing of the ethersolution gives 4.8 g. of raw product. Crystallization from benzene gives4.2 g. of needle-shaped crystals having a melting point of 108 C., thisyield corresponding to 46.8%, based on bis(cyclooctadiene)nickelcharged. The structure of the compound is confirmed by the IR and NMRspectra.

C, H analysis:

Calculated for C H O (percent): C, 67.7; M, 6.49. Found (percent): C,68.2; H, 6.52.

The alcohols obtained when hydrolyzing the nickel alcoholates which canbe prepared by the process of this invention and being alpha, omegabifunctional alcohols are useful for the preparation of polyesters withthe particular possibility to cross-link the resultant polyesters bymeans of the double bonds which are still contained in the bifuuctionalalcohols. Thus, any of the alcohols mentioned in the examples and in thespecification may be used directly and the nickel alcoholates aspreliminary products for the production of polyesters.

What is claimed is:

1. A process of preparing novel nickel alcoholates which comprisesreacting together at about 0 to 200 C. aldehyde or ketone compounds,1,3-diolefins and complexes of nickel (0).

2. Process according to claim 1, wherein said complexes of nickel (0)are prepared in situ.

3. Process according to claim 1, wherein said carbonyl compounds arealiphatic, alicyclic saturated and unsaturated aldehydes and ketones andsaturated and unsaturated aldehydes and ketones which are substituted byaromatic radicals, and corresponding dialdehydes and diketones.

4. Process according to claim 1, wherein said 1,3-diolefins arebutadiene or butadienes which are substituted by aliphatic, alicyclic oraromatic radicals.

5. Process according to claim 1, wherein the reaction is carried out attemperatures of from 20 to 200 C.

6. Process according to claim 1, wherein aliphatic, alicyclic oraromatic hydrocarbons, ethers or esters are used as solvents.

7. Process according to claim 1 wherein said 1,3-diole' fins or saidaldehyde or ketone compounds are used as solvents.

8. Nickel alcoholates of the general formula wherein R is hydrogen, a 1to 20 carbon atom-containing alkyl, alkenyl, alkinyl, aryl, substituted.aryl, arylalkyldiene, cycloalkyl( substituted cycloalkyl, alkoxyary andsubstituted alkyl, R and R are hydrogen, alkyl, substituted alkyl, arylor substituted aryl having up to 12 carbon atoms and wherein R and Rtaken together with the carbon atom to which they are attached can be ahydrocarbon cycloaliphatic ring having up to 12 carbon atoms therein.

9. Nickel alcoholate of octene-(4)-diol-(2,7).

10. Nickel alcoholate of 1,6-diphenyl-transhexene-(3)- diol-(1,6).

11. Nickel alcoholate of 1,10-diphenyldecatri-l,5,9-enediol-(3,8).

12. Nickel alcoholate of1,14dipheny1tetradecapentaene-(l,3,7,11,13)-di01-(5,l0).

13. Nickel alcoholate of the formula 14. Nickel alcoholate of2,7-dimethyloctene-(4)-diol- (2,7).

15. Nickel alcoholate of 1,4-di(cyclohexanolyl-1)butene-(2).

16. Nickel alcoholate of 2,7-diphenyloctene-(4)-diol- (2.7).

17. Nickel alcoholate of 1,6-diphenyl-(3)-methylhexene-(3)-diol-(l,6).

18. Nickel alcoholate of 1,6-diphenyl-(3,4)-dimethylhexene-(3 )-diol-(1,6)

19. Nickel alcoholate of 1,3,4,6-tetraphenyl-hexene- (3)-di0l-(1,6).

20. Nickel alcoholate of l,6-bis-(4-methoxyphenyl)- hexene- (3 -diol-(1,6)

21. Nickel alcoholate of 1,6-di-(p-dimethyl-aminophenyl)-trans-3-hexene-1,6-diol.

22. Nickel alcoholate of 1,6-di-(2-furyl)-trans-3-hexene-1,6-diol.

23. Process as claimed in claim 1, wherein said 1,3- diolefins have atleast one substantially non-reactive functional group selected from thegroup consisting of ethers, esters, acetyls, amines, and nitrilespendant therefrom.

24. Process as claimed in claim 1, wherein said carbonyl compound has atleast one substantially non-reactive functional group selected from thegroup consisting of Ethers, esters, acetyls, amines, and nitrilespendant there- References Cited UNITED STATES PATENTS 3,414,588 12/1968Jones 260340.7

OTHER REFERENCES Lohaus Chem. Abstracts vol. 49 (1955), col. 14651.Abstract of Chem. Ber. 87 (1954) pp. 1708-11.

-TOBIAS E. LEVOW, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R.

